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Patented Nov. 19, ‘1946
2,411,253
‘UNITED STATES
‘PATENT OFFICE
2,411,253
PEST CONTROL
- Albert L. Flenner and Norman E. Searle, Wil
" mington, DeL, assignors to E. I. du Pont de
Nemours & Company, Wilmington, Del., a cor
poration of Delaware
7N0 Drawing. Application October .11, 1941,
1
Serial'No. 414,608
9-Claims. (01. 167-22)
-
This invention relates to pest control and is
preference R. is a 2-thiazole radical, i. e., a thia
zole as de?ned in U. S. Patent 2,961,840 to E. K.
tions for controlling and preventing or arresting
Bolton (page 1, lines 21-39) attached at the 2
the development and growth of pestiferous or
position. Thus B. may be the 2-benz0thiazolyl
ganisms such as insects and fungi which infest, 5 or the 2-thiazolinyl radicals. In other impor
plant or animal matter either in the natural or
tant sub-groups R is alkyl or thioca-rbamyl, and
particularly directed to methods and composi
fabricated state, and particularly'to new insecti
cidal and fungicidal compositions and methods
characterized in .that the essential active agent
is an acyclic alpha-alamino sul?de.
'
In the control of pestiferous organisms which
- in each of the preferred cases X may be a methyl
ene radical either unsubstituted or bearing one
alkyl'f-group and Y, the amino group, unsubsti- ‘
10' tuted or.'substituted by aliphatic radicals.
The acyclic alpha-alamino sul?des may be
conveniently prepared by reacting together‘ a
thiol compound, an aliphatic aldehyde, and a
commonly infest living plants, inorganic poisons
and plant extractives are most commonly em
ployed. Inorganic materials suchv as arsenicals,
?uosilicates, sulfurs, coppers, and the like, while
usually cheap and generally effective lack many
primary or secondary aliphatic amine as illus
trated by the following equation:
.
‘
RI
desirable characteristics such as low toxicity to
R—ISH+R’CHO+R”R’ ."NH --> R-S-(‘JH-N R".R’ "+1110
warm blooded animals, lack of foliage injury un
der certain conditions, and lack of high speci?c
The reaction preferably may be carried out in
toxicity to certain types of organisms. Plant ex 20 the presence of a solvent such as one of the lower
tractives while highly effective toward_certain
alcohols.
classes of pests are expensive and generally spe
ci?c in their action. Except in a few isolated
cases synthetic organic chemicals have not been.
aldehyde are reacted together ?rst to form the
In some cases the thiol compound and
methylol sul?de followed by condensation with
the amine, which occurs with the splitting out
found generally applicable to the problems in 25 of water. In other cases the aldehyde may be
volved. Similar problems evincing similar need
reacted with the amine to form initially the
for new synthetic organic toxicants for the con
methylol amine, which may then be reacted with
trol of insects and fungi occur with respect to
the thiol compound. In most cases it is neces
those types of pestiferous organisms which com
sary merely to mix together equimolecular pro
monly infest fabricated plant and animal matter 30 portions of all three reactants in- a suitable sol
such as wood, textiles, leather, furs, rope and
vent and allow the reaction to take place at room
similar materials. Thus there is a need for new
temperature or at suitable elevated temperatures.
synthetic organic pest-control agents which may
The products are often crystalline solids that may
be compounded as insecticides and fungicides for
be easily puri?ed by recrystallization. Examples '
combatting the various problems in the art.
35 of the preparation and utilization of acyclic al
pha-alamino sul?des in pest control compositions
We have now discovered a new class of syn
thetic organic pest-control agents, many mem-,
are given below.
bers of which maybe synthesized readily from
EXAMPLE 1
such cheap and available raw materials as
.amines, aldehydes, thiols, carbon disul?de and 40 z-Bimzornmzonxr. N-PIPERIDYLMETHYL SULFIDE
the like. This class is constituted by those or
This compound may be obtained according to
ganic compounds which have an aliphatic amino
the following reaction: »
group (alamino group) linked through amino ni
N
trogen to an alpha carbon atom of an organic
\ C-SH + HaCO + OH:CHz-CH:
sul?de and in which the N-C-S group is not 45
I
NH —-->
part of a heterocyclic ring, or more simply the
acyclic alpha-alamino sul?des.
‘
~
S
The class may be represented by the formula
50
in which R is an organic radical attached to S
through carbon, X is a methylene radical bear
ing at least one hydrogen, and Y represents an I v
aliphatic substituted or unsubstituted amino rad
A mixture of
ical linked through amino nitrogen to X. By 65 -zole, 6.5 parts
N
\
CHI-C
/
I
CH 2- CH I
_ C—S—CH2—N\
OH: + 1120
8/
CHE-CH:
13 parts of Z-mercaptobenzothia
of piperidine, and 10 parts of 37%
2,411,268
that separates is crystallized from ethyl alcohol
after which it consistslof yellowcrystals melting
at 114-6° C. This product contains by analysis
10.46% nitrogen and 24.79% sulfur.
- A water-dispersible pest-control composition
may be prepared by milling 80 parts of 2-benzo
thiazolyl N-piperldylmethyl sul?de with 20 parts
of Bancroft clay. When applied as a 1:200 aque
4
ble in all the common organic‘solvents including
the hydrocarbon oils.
aqueous formaldehyde in ethyl alcohol as a sol
vent is allowed to stand overnight. The product
Dimethylaminomethyl dimethyldithiocarbam
ate‘may b'e-prepared for pesticidalapplications
:1
by grinding one part of the active ingredient to
gether with 2 parts of bentonite. When this
composition was made into an aqueous disper
sion of 1/2% concentratlon'and sprayed onto bean
plants very little feeding 'by‘Mexican bean beetle
10 adults was observed while 80% of the insects
were destroyed. This performance is equal to
that given by the lead arsenate control.
Mexican bean beetles and Japanese beetles. The
usefulness ofthis aminomethyl sul?de as a fungi
EXAMPLE 4
cide and preservative is illustrated by the data
2-Bunzornmzotxr. N-Moarnonmomsrnxr.
15
of Table I.
S'ULI‘IDE
EXAMPLE 2
A mixture of 33.4 parts of 2-mercaptobenzothi
z-Bsnzormszonxr. MIrHYLrmmNoMsn-iirr.
azole, 160 parts of methanol, and 16.2 parts of
Sorrrnr.
37% aqueous formaldehyde is warmed until a
This compound is prepared according to the 20 clear solution is obtained. Then 17.4 parts of
following equation.
morpholine is added and the solution boiled for
10 minutes. On cooling 46 parts of a. yellow
ous spray this composition acts as a repellent for .
crystalline solid separates. After recrystalliza¢
tion from carbon tetrachloride this aminomethyl
25 sul?de melts at 148-150? C. and contains by
. ‘analysis 10.44% nitrogen.
2-benzothiazolyl N-morpholinomethyl sul?de
is an e?ective insectifuge for protecting bean
plants from Mexican bean beetles. A suitable
30 dust for this application is prepared by mixing
S
One process for'preparing the desired amino
methyl sul?de is as follows: A mixture or 66.8
parts of 2-mercaptobenzothi'azole, 240 parts of
methanol, and 36 parts of 28% aqueous ammonia
is stirred until a clear solution is obtained. IWith
1 part of the aminomethyl sul?de dissolved in a
convenient amount of acetone with 99 parts of
talc and evaporating the pasty mass to dryness,
after which the composition is comminuted by
ball milling. Although this composition was not
appreciably lethal to the Mexican bean beetle
larvae it was at least 90% effective in preventing
good stirring and suillcient cooling to maintain
feeding.
'
the temperature at 5-10” 0., 100 parts of 37%
EXAMPLE 5
aqueous formaldehyde diluted with 100 parts of 40
DODECYLAMINOMETHYL 2-THIAZOLINYL SULFIDE
water is slowly added. The precipitated amino
methyl sul?de is then washed with water, am
This compound is obtained upon adding a solu
moniacal alcohol, and ether after which the prod
tion 27.8 parts of dodecylamine in 20 parts of
uct is dried in vacuo. A yield of 62 parts of light
methanol to a hot solution of 17.9 parts of 2
yellow powder melting with decomposition at
mercapto-2-thiazoline and 12.2 parts of--37 per
about 100-120° C. is obtained. The sulfur con
cent aqueous formaldehyde in 60- parts of meth'-'
tent by analysis is 32.0%.
anol. The oily mixture which precipitates is
Z-benzothiazolyl methylenaminomethyl sul?de
heated at the boil with stirring for ten minutes,
is an effective fungicide and preservative as
cooled, and ?ltered. The residue amounting to
indicated by the data of Table I.
42 parts consists of soft, waxy crystals melting at
39-42’ 0. containing 8.69 per cent nitrogen by
EXAMPLE 3
analysis.
A dust suitable .for insecticidal applications
DIMETHYLAMINOMETHYL Drmn'ri-rYLnrrnro-v
CARBAMATE
may beprepared by mixing one part of dodecyl
aminomethyl 2-thiazolinyl sul?de with 99 parts
This aminomethyl sul?de is of the thioester’
of tale in the presence of su?icient acetone to
type and may readily be obtained as follows:
make a smooth uniform paste. Upon drying the
caked mass is ground into a fine powder com
prising the active constituent coated onto the
60 talc. Used to control Mexican bean beetle lar
vae on bean plants, this dust gave a 93% kill and
allowed 5% foliage consumption under rigorous
To a solution of 90 parts of dimethylammonium
dimethyldithiocarbamate in 90 parts of water,
45 parts of 37% aqueous formaldehyde solution
laboratory conditions. In direct comparison a
1% calcium arsenate dust made up with talc gave
80% kill and allowed 5% foliage to be eaten.
Dispersions of dodecylaminomethyl Z-thiazolin
yl sul?de in water show aphicidal activity. Such a
dispersion may be prepared by diluting 1 part of a
cooling to maintain the temperature at 0° C. The
solution containing 2.5% of the thiazolinyl sul?de
product immediately precipitates as a white crys
talline material, which is ?ltered off, washed with 70 and 0.25% of the sodium salt of sulfated technical
ice water, and air ‘dried. The crude product ‘ oleyl acetate, prepared as described in Example I
of U. S. Patent 2,163,133 in acetone with 24 parts
amounts to 73.6 parts of white crystals melting at
' of water. Sprayed on a mixed culture of Aphis
35-37° C. After recrystallizing from ether, the
rumicis and Myzus persicae on nasturtium plants,
melting-point is raised to 38-9° C. The product
contains by analysis 35.64% sulfur and is solu 75 this solution e?ected an 87% kill of the former
is slowlyvadded with good stirring and sufficient
‘
2,411,2ss
6
and a 93% kill of the latter. Practically’ no kill
moth larvae were destroyed while only 1% or less
of the surface nap was visibly damaged. Under
is obtained with a. similar composition in which
the thiazolinyl sul?de is omitted.
the same conditions the untreated check was dam
The effectiveness of dodecylaminomethyl 2
aged to the extent of 73%.
thiazolinyl sul?de as a fungicide and preservative
may be noted from the data of Table I.
.
EXAMPLE 6
4-MoRPHoLrNoMEr1-IYL ‘Z-THIAZOLINYL SULFIDE
This compound is obtained as follows: A mix
'
The acyclic alpha-alamino sul?des of this in
vention exhibit unusual utility as fungicides and
preservatives.
The data of Table I are illustra
‘ tive. These data were obtained by making a dis
perslon of the fungicide in sterile liquid malt agar
10
ture containing 23.8 parts of 2-mercapto-2-thi
(pH of 5.7) followed, after hardening, by inocula
tion with a; suspension of the appropriate fungus
organism.
azoline and 16.2 parts of 37% aqueous formalde
hyde in 80 parts of methanol is warmed with stir
.
Table
ring until solution is effected. Then 17.4 parts
of morpholine is slowly added with caution since 15
considerable heat is evolved. When the reaction
Acyciic sminomethyl sul?de
subsides, the mixture is heated at the boil for 5
minutes. Upon cooling-the product separates as
'
I
I
-
Concentration effective ‘
against
Penicillium
lumber mold
white crystals, which are ?ltered off and recrys
tallized from methanol. The yield is 36 parts of 20 Benzothiazolyl piperidylmethyl sul?de.
l :4, 000
‘recrystallized product melting at Ill-3° C. and
Be?lzgghiazolyl methyleneminomethyl
1:1, 000
containing by analysis 29.66% sulfur (the theo
Dimethylaminomethyl diniethyldi118,000
retical value is 29.36%‘).
,
Benzothiazolyl N-morpholinomethyl
An insecticidal dust is prepared by grinding to
sulfide .................... .; ...... _.
114,000
gether 80 parts of 4-morpholinomethyl 2-thia 25 Benzothiazolgl
dicylohexylaminc=
s
'
zolinyi sul?de, 14 parts of trlcalcium phosphate,
5 parts of bentonite, and 1 part of “Lorol” alco
hol. This water-dispersible powder may be used
in aqueous sprays or dusts. When diluted with
talc soas to yield an active ingredient concentra
tion of 0.5% and applied to bean plants infested
with Mexican bean beetle larvae, 93% of the in
sects were destroyed while only 5% of the foliage
e ............................ ..
nicer
.
1:8, 000
1:1, 000
1:4,000
thiocarbamate ..................... __
methyl sul de ..................... ..
1:4,000
1 4,000
114,000
Dodecglerninomethyi
2~thinzolinyl
sul? e ............................ __
114,000
1:4,000
py] sul?de ......................... ..
1:1, 000
1:1, 000
dithiocarbamate ................... ..
1:1,000
1:1,000
?de _______________________________ _.
1:250
1:1,000
beta-Hydroxyethylaminometbyl pro
N-morpholinomethyl oxydiethylene-
30
Aapemillm
N-morpholinomethyl 2-thiazolinyl sul
Dicyclohexylaminornethyl
~
2~thiazo-
linyl sul?de....................... . .
Piperidylmethyl 2_thiazolinyl sulfide.
'
1:250
1:250
1:250
1:250
was consumed. ‘The calcium arsenate control at
the same concentration allowed approximately
The foregoing are representative of various
methods and compositions. It is to be under
stood, however, ‘that the invention is in no wise
limited thereto and that the active agents may
be made by other methods, may be compounded
in other ways and applied for the control of other
the same proportion of foliage to be consumed
while effecting a kill of 73%.
This alpha-alamino sul?de may be formulated
into mothproo?ng compositions of unusual effec
tiveness. In tests in which standard woolen test
fabric was impregnated from 2% solution in ace-v
types of insects, pests and microorganisms. By
‘means of methods analogous to those described
tone and then dried and exposed to attack by vig
orous moth larvae for two ‘weeks 100% of the
moth larvae were destroyed while only 1% or less
of the surface nap was visibly damaged. Under
the same conditions the untreated check was dam
aged to the extent of 56%.
EXAMPLE 7
v
DICYCLOHEXYLAMINOMETHYL 2-THIAZOLINYL
'
Somme
'
This compound is obtained upon adding 27.2
parts of dicyciohexylamine to a warm solution
above, a, wide variety of products may be obtained
in which R in the general formula R-S-X-Y,
in addition to benzothiazolyl, thiazolinyl, alkyl,
and thiocarbamyl as already’ described, may be
aryl, such as phenyl, tolyl, naphthyl, and their
50
common halogen and nitro substitution products ;
aralkyl, such as benzyl; cycloalkyl, such as cyclo
hexyl; alkenyl, such as allyl, crotyl, cyclohexenyl;
straight or branched aliphatic chains of from 1
to 24 carbon atoms and their halogen and nltro
substitution products,_such as methyl, amy'l, 2
ethylhexyl, dodecyl; acyl, such as benzoyl or
of 17.9 parts of 2-mercapto-2-thiazoiine and 12
parts of 37 per cent aqueous formaldehyde in 80 55 acetyl; ‘and thioacyl, such thioacetyi or thic
parts of methanol.‘ The solution is brought to a
benzoyl. Bifunctional acyclic alpha-alamino sul
boil and then cooled to throw down the white
?des such as would exist if R were bifunctional'
crystalline product (90 per cent of theory). It
as, for ‘example, Y-X—S—CHaCH2-—S—X—-Y,
consists of colorless needles melting at 109-111°
are included. The X group may vary also accord
C. and contains 20.35 per cent sulfur by analysis. 60 ing to the nature of the aldehyde and may in
A composition suitable for dispersing in water
clude the substitution of one methylene hydrogen
is prepared by milling together 80 parts of di
cyclohexylaminomethyl 2-thiazoliny1 sul?de, 14
as by a lower alkyl group, such as methyl, ethyl,
propyl, isopropyl, and the like. Thus X may be
parts of tricalcium phosphate, 5 parts of bento
ethylidene, propylidene, and isobutylidene. The
nite, and 1 part of “Lorol” alcohol. When sprayed 65 alamino radical may be either unsubstituted or
on apples at an active ingredient concentration
substituted by aliphatic substituents.
Suitable
of 4 lbs./ 100 gallon, 87.5% control of codling moth
substituted alamino groups include methylamino,
was obtained, whereas under the same conditions
diethylamino, hexamethylenimino, dioctylamino,
lead arsenate gave 50% control.
betahydroxyethylamino. and ‘the like. Y may also
This alpha-alamino sul?de may be formulated 70 be alamido, though it appears generally that com
into mothproofing compositions of unusual effec
pounds of this type are relatively inferior. Thus,
tiveness. In tests in which standard woolen test
the alamido. sul?des, N-(2-benzothiazolyltlhio
fabric was impregnated from 2% solution' in ace
tone and thenvdried and exposed-to attack by
vigorous moth larvae for two weeks 100% of the
methyl) -epsilon-caprolactam, N- (2-benzothiazol
ylthiomethyl) - caprylamide, N -(ethy1thiometh
yD-epsilon-caprolactam, and N-(ethylthiometh
9,411,958
ticular usefulness in special applications and fre
yl) lauramide show only mild toxicity as compared
" with the alamino sul?des.
quentlyawill give better results than would be
anticipated from the killing power or repellent
'
The parasiticidal agents of this invention may
be used as fungicides, insecticides, insectifuges,
foliage protectants, mothproo?ng agents, aphi
cides, and as the toxic ingredients in baits. They
are particularly useful for protecting textile ma,
action of each ingredient when used alone.
Thus the active agents of this invention'may
be formulated in a wide variety of ways as may
,be best suited to the control of any particular
terials from the ravages of clothes moths and
pest or combination of pests having in mind the
and fungous decay and putrefaction of such ma
materials as have been mentioned,‘ etc., such as
carpet beetles, and for protecting growing plants ' nature of'the pests, their particular habitat and
and foliage from depredatory insects such as the [10 feeding habits andtheir peculiar susceptibilities,
if any. Thus suitable compositions maybe pre
Mexican bean beetle, the Colorado potato beetle, . pared
with the active agent in a state of com
the Japanese beetle, and the like. The agents of
this invention ‘may be used to prevent bacterial , position, subdivision, association with such other
terials as rawhides, glues, gelatins, carbohydrate 15 may be necessary peculiarly to adapt the active.
agent to the purpose to be effected.
'
pastes, rope, lumber, fabrics, and other materials,
We claim:
either natural or manufactured; that are subject
1. A parasiticidal composition containing as
to attack anddecomposition‘ by microorganisms.
an essential active ingredient the compound hav
These products may also be used for the control
of mildew and other fungous diseases to which 20 ing the formula R-S-IX-Y in which R is a
thiazole attached at the 2-position, X is a meth-.
living plants are subject.
v
ylene radical hearing at least one hydrogen and Y
They may be used in various combinations with
represents an aliphatic substituted or unsub
such auxiliary materials as spreaders, stickers,
stituted amino radical linked through amino ni
and other toxicants; for example, insecticides
such as metallic arsenates, ?uosilicates, pheno 25 trogen to X, and a carrier therefor.
' 2.- A parasiticidal composition containing as
thiazi-nes, organic thiocyanates, such as n-dodecyl
an essential active ingredient a 2-benzothiazolyl
thiocyananate and butyl carbitol thiocyanatep
alpha-alamino methyl sul?de and a carrier
nicotine, anabasine (neo-nicotine) norsnicotine,
therefor.
‘
rotenone and its congeners, hellebore, pyrethrum,
N-isobutylundecylenamide, aminomethyl sulfides, 30 3. A process for protecting material from at
tack by insects and pestiferous micro-organisms
and bactericides and fungicides such as sulfur,
which comprises treating the material with a
polysul?des such as lime-sulfur, thechlorinated
phenols, aminomethyl sulfides, copper acylacet
onates, copper chelates of beta-keto acids and
esters, copper chelates of salicylaldehyde, Bur
compound having the formula R-—S—X-Y in
which R. is a thiazole attached at the 2-position,
gundy mixture, Bordeaux mixture, the so-called
Xis a methylene radicalbearing at least 1 hy
drogen, and Y represents an aliphatic substituted
insoluble copperssuch as basic copper sulfates,
copper oxychlorides, copper calcium chlorides,
amino nitrogen to X.
or unsubstituted amyl radical linked- through
-
4. A process for protecting material from at
copper oxides, copper silicates, copper zeolites,
and copper thiocyanates, the long chain quater 40 tack by insects and pestiferous micro-organisms
which comprises treating the material with a 2
nary ammonium halides and derivatives of di
benzothiazolyl alpha-alamino methyl sul?de.
thiocarbamic acid such as ferric dimethyldithio
5. A parasiticidal composition containing as an
carbamate. They may be used in the form of
essential active ingredient an acyclic alpha
aqueous sprays, dusts .or solutions, dispersed with
wetting agents such as the alkali metal or amine 45 alamino sul?deeand a carrier therefor.
6. A process for protecting material from at
salts of oleic acid and the sulfated higher alco
tack by insects and pestiferous micro-organisms
hols, the sulfonated animal and vegetable oils
which comprises treating the material with an
such as sulfonated ?sh or castor oils or the sul
acyclic alpha-alamino sul?de.
fonated petroleum oils; with diluents such as
calcium phosphate, Bancroft clay, kaolin, diat 50 'l. A parasiticidal composition containing as an
essential active ingredient ,2-benzothiazolyl N
omaceous earth, sulfur, lime, pyrophyllite, talc,
piperidylmethyl sul?de and a carrier therefor.
bentonite, ?ours such as walnut shell, wheat,
8. A parasiticidal composition containing as an
redwood, soya bean, cottonseed, or with organic
essential active ingredient dimethylaminomethyl"
solvents such as trichloroethylene, tetrachloro
dimethyldithiocarbamate and a carrier therefor.
ethylene, Stoddard solvent, and other hydrocar
9. A parasiticidal composition-containing as an
bon solvents. They may be used in vegetable and
mineral oil sprays in which petroleum or vege
table 011 glycerides are used as contact agents or
active poisons. Various adhesive and sticking
materials such as rosin and glue and various other 60
common adjuvants such as lime may be used.
Such mixtures as are here set out may have par- -
essential active ingredient dodecylaminomethyl
2-thiazoliny1 sul?de and'a carrier therefor. ‘
ALBERT L. FLENNER.
NORMAN E. SEARLE.